US3607763A - Process for the preparation of laundering compositions - Google Patents
Process for the preparation of laundering compositions Download PDFInfo
- Publication number
- US3607763A US3607763A US878989A US3607763DA US3607763A US 3607763 A US3607763 A US 3607763A US 878989 A US878989 A US 878989A US 3607763D A US3607763D A US 3607763DA US 3607763 A US3607763 A US 3607763A
- Authority
- US
- United States
- Prior art keywords
- percent
- sodium
- softener
- mixture
- spray
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000004900 laundering Methods 0.000 title description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 17
- 239000010452 phosphate Substances 0.000 claims abstract description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 16
- 239000003085 diluting agent Substances 0.000 claims description 16
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 15
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 15
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- 239000003599 detergent Substances 0.000 abstract description 34
- 238000001694 spray drying Methods 0.000 abstract description 16
- 239000004753 textile Substances 0.000 abstract description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 abstract description 4
- 239000007970 homogeneous dispersion Substances 0.000 abstract description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 abstract description 2
- 235000011009 potassium phosphates Nutrition 0.000 abstract description 2
- 239000001488 sodium phosphate Substances 0.000 abstract description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 description 17
- 238000001879 gelation Methods 0.000 description 14
- 235000021317 phosphate Nutrition 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 150000001340 alkali metals Chemical class 0.000 description 9
- -1 thiophenols Chemical class 0.000 description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 description 8
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000013799 ultramarine blue Nutrition 0.000 description 4
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical group [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 3
- 235000021286 stilbenes Nutrition 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical group COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- PTMRDOLOEDPHLB-UHFFFAOYSA-N 2,3-dipentylphenol Chemical compound CCCCCC1=CC=CC(O)=C1CCCCC PTMRDOLOEDPHLB-UHFFFAOYSA-N 0.000 description 1
- NYUCPFMRQPYIRQ-UHFFFAOYSA-N 2,4-dicyclohexylphenol Chemical compound OC1=CC=C(C2CCCCC2)C=C1C1CCCCC1 NYUCPFMRQPYIRQ-UHFFFAOYSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N 3-Pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- FUXZRRZSHWQAAA-UHFFFAOYSA-N 5,5-dioxodibenzothiophene-3,7-diamine Chemical compound C1=C(N)C=C2S(=O)(=O)C3=CC(N)=CC=C3C2=C1 FUXZRRZSHWQAAA-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002752 cationic softener Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- LVXHNCUCBXIIPE-UHFFFAOYSA-L disodium;hydrogen phosphate;hydrate Chemical compound O.[Na+].[Na+].OP([O-])([O-])=O LVXHNCUCBXIIPE-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940037395 electrolytes Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002190 fatty acyls Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 239000011021 lapis lazuli Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical class [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 235000001508 sulfur Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/02—Preparation in the form of powder by spray drying
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- a process for the preparation of a spray-dried, built, detergent-softener composition containing an ethoxylated nonionic detergent in combination with a di-higher alkyl quaternary ammonium textile softener which comprises the steps of( l admixing the softener, nonionic dctergent, and water to form an aqueous mixture containing a homogeneous dispersion of the softener; (2) incorporating an inorganic sodium or potassium phosphate builder in the aqueous mixture of step i to form a mixture containing more than 50 percent solids by weight, the temperature of the mixture being at least about 180 F. at the time the phosphate is introduced therein, and (3) spray drying the mixture of step 2.
- a PROCESS FOR THE PREPARATION OF LAUNDERING COMPOSITIONS This invention relates to the preparation of laundering compositions and more particularly to a process for preparing spray-dried granular laundering compositions.
- the practice has been to form the components of the softener composition into granules and mix these granules with detergent composition granules to produce a commercial package.
- This is usually accomplished by using a three-step process, which merely means that the softener granules and the detergent granules are prepared separately by crutching and spray drying and the two kinds of granules are subsequently blended to produce the product.
- the three-step" process as the term is used in the industrial sense is not given a literal interpretation.
- the first two steps are complete processes within themselves for crutching and spray-drying a particular composition, in this case a softener or detergent composition.
- the third step is concerned with the blending of the two components.
- a one-step process was then attempted in order to eliminate the need for extra equipment and cut the process time by preparing the softener and detergent in a form whereby each granule contained by proportionate share of softener and detergent. It was felt that this process would also reduce segregation and contribute to a higher uniformity of product.
- an object of this invention to provide an economical one-step process for the preparation of spraydried softener-detergent granules based on an amount of crutcher solids which is more than 47 percent by weight and preferably about 59 to about 65 percent by weight.
- a further object is to provide a process whereby the spraydried softener-detergent granules are such that the softener and detergent compositions are combined in each granule in a homogeneous relationship.
- an inorganic water soluble diluent to provide bulk and an alkali carboxymethyl' cellulose as an antiyellowing agent, be added. So long as the temperature of the mixture is at least 180 F., and the quaternary salt is dispersed, the order of addition of the alkali metal phosphate and the inorganic water soluble diluent (elec trolytes) is immaterial.
- the alkali metal carboxymethylcellulose can be added at any point of the process.
- the spray-dried product of this invention has been found exceptionally satisfactory in the following parameters: solubility, free flow, low dust content, storage, narrow distribution of particle sizes, bulk density, residual moisture content, and color.
- the granules which, as previously mentioned, contain a homogeneous mixture of softener-detergent composition, are hollow and have sufficient strength to resist the stress and strain of handling which take place throughout the processing, packaging, and delivery stages of their commercial life.
- the final cup weight of the commercial product is preferably from about 60 to 125 grams, flowability about 70 percent to about percent, and particle size about 16 to about 60 mesh. Cup weight is based on a cup which holds 237 grams of water.
- the first part of the process is carried out in conventional crutching apparatus wherein initially water, a water-soluble nonionic detergent, and a quaternary ammonium salt are introduced simultaneously or in any order which is desirable to the operator.
- the preferred order is that stated.
- nonionic detergents can be used in the process of this invention, but are preferably in liquid or paste form.
- nonionics have a hydrophobic group containing at least 8 to 30 carbon atoms.
- One particular class of such detergents is that formed by the oxyalkylation of fatty acids, alcohols, phenols, mercaptans, thiophenols, amines, and with ethylene oxide, propylene oxide, and other related alkylene oxides.
- Such materials usually have at least 5 mols of alkylene oxide, and preferably 5 to 30 mols of alkylene oxide, depending upon the particular hydrophobic group desired. Representative of these materials are those formed by condensation of ethylene oxide with alkyl phenols or alcohols.
- condensates formed by the reaction of one mol of nonyl phenol or a mixture of C -C saturated, straight-chain, aliphatic alcohols with 8 to l2mo1s of ethylene oxide, the condensates containing an average of about 8 to ethylene oxide groups per molecule.
- nonionic detergent examples include as follows: nonyl phenol-ethylene oxide condensates having an average of 9.5 ethylene oxide groups per molecule; a mixture of saturated aliphatic alcohols having from 14 carbons to l8 carbons in their chains and an average of 8.5 mols of ethylene oxide per molecule; tallow alcoholethylene oxide condensate having an average of 9 mols of ethylene oxide per molecule; and a 1:1 mixture of a C and a C saturated aliphatic alcohol having an average of 8.5 mols of ethylene oxide per molecule.
- alkylphenol condensates are those of diamylphenol, p-tert-octylphenol, 2,4- dicyclohexylphenol, m-pentadecylphenol, and benzyl-ohydroxybiphenyl.
- Other condensates with alkylene oxide are those of tall oil, branched chain C to C,-, aliphatic alcohols, lanolin, beeswax, bis-phenols, oxidized paraffin wax, napthenic acids, and fatty acyl alkanolamides. Mixtures of various water soluble nonionic detergents are contemplated.
- the quaternary ammonium slat softener can be exemplified by the following general formula:
- R and R are alkyl groups each containing from 1 to 3 carbon atoms; R and R are aliphatic groups each containing from 12 to 22 carbon atoms; and X is selected from the group consisting of chlorine, bromine, and methyl sulfate. These compounds are readily dispersible in water.
- distearyl dimethyl quaternary ammonium chloride distearyl dimethyl quaternary ammonium bromide; distearyl dimethyl quaternary ammonium methylsulfate; dicoco dimethyl quaternary ammonium chloride; dimethyl arachidyl behenyl quaternary ammonium chloride; dialkyl dimethyl quaternary ammonium chloride, the alkyl groups of which comprise a mixture consisting essentially of 24 parts hexadecyl 75 parts octadecyl and 1 part octadecenyl groups; the latter quaternary ammonium chloride is also known as dimethyl dihydrogenated ditallow ammonium chloride and is particularly preferred.
- coco refers to fatty acid groups formed in coconut oil fatty acids. Such acids contain from about 8 to about 18 carbon atoms per molecule, predominating in C C acids).
- Other examples are dimethyl ditallow hydrazinium chloride and dimethyl ditallow quaternary ammonium methyl sulfate.
- the proportions of the foregoing components which can be used are as follows: waterabout 33 percent to about 43 percent and preferably about 35 percent to about 41 percent; nonionic detergentabout 3.5 percent to about percent and preferably about 4.5 percent to about 8.5 percent; quaternary ammonium salt-about 1 percent to about 6 percent and preferably about 2.5 to about 4 percent. These percentages are by weight and based on the total weight of the initial materials as introduced into the crutcher. The proportions of the other components will be set forth below.
- the quaternary ammonium salt be homogeneously dispersed in the mixture before the phosphate builder is added. This is accomplished by heating or agitation caused by merely admixing the water, nonionic, and quaternary salt or by external means. Both agitation and heating are discussed below.
- the homogeneous dispersion of the quaternary ammonium salt bears a similarity to a melt or solution of the salt in the water and nonionic.
- Agitation which is preferred and practical, can be initiated before, during, or after the water, nonionic detergent, and quaternary ammonium salt are introduced into the crutcher.
- the speed of agitation can range from about 100 revolutions per minute (r.p.m.) to about 500 r.p.m. and preferably from about r.p.m. to about 400 r.p.m. and can be varied during the course of the process.
- the given rates are based on the used of conventional equipment. Actually, any reasonable movement or agitation of the mixture will suffice to carry out the process of this invention so long as it commences before or at the same time as the addition of the second group of components, although high shear agitation is not practical.
- the materials in the crutcher should be a temperature of at least about 180 F. It is preferred to initially heat the first group of materials (water, nonionic, and quaternary salt) about 130 F. to about F; however, there is no prohibition against raising the temperature at any time before the second group of materials is added. The particular mode of heating is not important and can be accomplished with whatever heating apparatus is available so long as the temperature can be ascertained. Once the temperature of the mixture has been raised to at least 180 F. and the quaternary salt is homogeneously dispersed, the second group of components can be introduced into the crutcher. There is actually no upper limit for the temperature of heating the crutcher materials other than keeping the temperature below the boiling point of water (212 F.).
- the most practical temperatures are from about 180 F. to about 200 F. and preferably from about 180 F. to about 190 F. If the ternperature is less than 180 F. and particularly about F. or less, gelation occurs after one or more of the second group of components is introduced to obtain more than 47 percent solids. It should be noted that between 175 F. and below about F. there is a gray area in which gelation is not sharply apparent, but is sufficient to hamper economical spray-drying. By heating to at least about 180 F., this partial gelation is also avoided.
- the quaternary salt homogeneously dispersed, the alkali metal phosphate, the inorganic water-soluble diluent, and the alkali metal carboxymethylcellulose can be introduced into the crutcher.
- this second group has no particular order of introduction and each component can be introduced one at a time or the entire group can be added simultaneously, although preferably the order stated is the order followed. Agitation can be continued until a homogeneous mixture is attained.
- alkali metal phosphate builder salts examples include the alkali metal tripolyphosphates and pyrophosphates of which the sodium and potassium compounds are most commonly used. These phosphates are well known in the detergent art as builders and can either be used alone or as mixtures of different phosphates. More specific examples of phosphate builder salts are as follows; sodium tripolyphosphate; sodium phosphate, tribasic; sodium phosphate, monobasic; sodium phosphate, dibasic, sodium pyrophosphate; sodium pyrophosphate; acid. The corresponding potassium salts are also examples of satisfactory builders for use herein along with mixtures of the salts or corresponding mixed potassium-sodium salts.
- a low phase l material is preferred, i.e., a phase 2 tripolyphosphate associated with a maximum of about 8 percent phase 1 tripolyphosphate, the phase 1 crystalline form being a high temperature rise material with hydrates more rapidly than the phase 2 material.
- the preferred tripolyphosphate form is conventional for spray dry ing operation and was used in Example I, below.
- an inorganic water soluble diluent can be used which is exemplified by the preferred alkali metal (generally Na or K) sulfates such as sodium sulfate. These preferred diluents generally do not provide any substantial detersive activity. Other examples of diluents are sodium chloride and sodium carbonate.
- Diluents such as the silicates exemplified by sodium metasilicate and sodium silicates wherein the ratio of Na O to SiO is from about 1.621 to about 3.2:1; borax; clays such as kaolin, the montmorillonites, and bentonites; silica sol; titanium oxide; colloidal aluminum hydroxide; and ammonium carbonate can also be used; however, it is preferred that the major proportion of the diluent be an alkali metal sulfate, which can be considered an inert material.
- the third component of the second group is an alkali metal (generally, Na or K) carboxymethylcellulose, in particular those having about 0.5 to about 0.8 carboxymethyl group per cellulose unit.
- This component is considered an organic builder and as noted in U.S. Pat. No. 3,360,470 referred to above provides the antiyellowing efiect for the quaternary ammonium softener.
- the proportions of the second group of components which are by weight based on the total weight of components introduced into the crutcher are as follows: alkali metal phosphate builder salt-about 13 percent to about 45 percent and preferably 27 percent to 33 percent; dilventabout 7 percent to about 25 percent and preferably 17 percent to about 23 percent; and an alkali metal carboxymethylcellulose about 0.3 percent to about 4.5 percent and preferably about 0.7 percent to about 2.5 percent.
- the proportions should be selected in a corresponding ratio so that there will be a sufficient amount of each component to provide more than 47 percent solids in the crutcher composition. It should be noted that even through 59-60to 65 percent solids are generally considered the most desirable for spray-drying, all of the solids percentages above 47 percent and preferably about 50 percent are important because the bulk density of the composition after spray-drying is dependent upon the percentage of solids resulting from the crutching operation. Although it is not generally the case, there are some instances when it is commercially necessary to achieve a bulk density which will result from a lower solids percentage. However, this does not in any case normally go below the 50 percent solids level. About 65 percent solids is the upper practical limit for spraydrying because the high solids content becomes too difficult to pump; however, higher levels of solids can be crutched within the process of this invention, if desired.
- Crutching time is generally from about 5 minutes to an hour or more with about 20 to 40 minutes being most desirable. Time is not critical and it has been found that about 30 minutes provides satisfactory homogeneity. Times greater than an hour provide no advantage and shorter than 5 minutes contribute to waste because of settling.
- the spray-drying equipment used is just as conventional as the crutching equipment. It includes spray nozzles, a high pressure pump, an air spray system, a heater for the air, and a dust separator. Two types of systems make use of this equipment. They are known as parallelcurrent and countercurrent drying and of these two systems the countercurrent system is the most desirable; however, in many cases, both systems are used to take advantage of each.
- colorants perfumes, brighteners, and bluing agents can be added if desired.
- the amounts of these substances introduced into the softener-detergent composition are obviously such that they will not adversely affect the desired properties.
- the amounts of all of these substances taken together add up to less than 2 percent by weight of the total weight of the crutcher composition and preferably less than 1 percent.
- the colorants are usually in the form of dyes.
- the brighteners are stilbene, triazole, and benzidine sulfone compositions, the stilbene and triazole compositions in combination being preferred. These components are, of course, not an essential part of the softener-detergent composition used in the process of this invention.
- the colorant and perfume are preferably added during or after spray-drying whereas the brighteners are added to the crutcher mixture.
- the bluing agent is usually added to the crutcher mixture after the water and it is a preferred component because of its antiyellowing contribution.
- An example of a bluing agent is ultramarine blue which has been found to be stable to light, alkali, and bleach and is insoluble in water.
- Ultramarine blue is a well-known blue pigment occurring naturally as the mineral lapis lazuli and can be synthesized by igniting a mixture of kaolin, sodium carbonate or sulfate, sulfur, and carbon. The micropulverized, synthetic ultramarine blues have proved satisfactory.
- the proportions of components which can be present in the final product in percent by weight based on the total weight of the final composition are as follows: waterabout 5 percent to about 15 percent and preferably about 6.5 percent to about 12.5 percent; nonionic detergentabout 5 percent to about 30 percent and preferably about 7 percent to about l2 percent; quaternary ammonium salt-about 2 percent to about 8 percent and preferably about 4 percent to about 6 percent; alkali metal phosphate builder salts about 20 percent to about 65 percent and preferably about 40 percent to about 48percent; dilventabout 10 percent to about 37.5 percent and preferably about 25 percent to about 35percent; an alkali metal carboxymethylcelluloseabout 0.5 percent to about 5.33 percent and preferably about 1 percent to about 3.5 percent; colorant, perfumes, brighteners, and bluing agentstotal weight 0 percent to about 2 percent and preferably 0 percent to about 1 percent; bleaching agent-0 percent to about 10 percent and preferably 0 percent to about 5 percent.
- CMC carboxymethylcellulose
- CMC carboxymethylcellulose
- stilbene brightener a triazole brightener agitation (350 rpm), after which the CMC and the brighteners were added. The crutching time was 30 minutes.
- the slurry was then pumped with a triplex pump into a spray tower where it was met with a countercurrent of hot air.
- the dried particles dropped to a conveyor and were transported to an air lift, which passed the granules along to a separator. Screening, perfuming, and packaging followed.
- EXAMPLE 11 The same crutcher steps and conditions as in example 1 are followed except the order of addition was water, blue, sulfate, silicate, tripolyphosphate, nonionic detergent, CMC and brighteners, and quaternary ammonium salt. Agitation is used for all ingredients except the nonionic detergent. The 180 F. temperature was invoked before the addition of sulfate.
- EXAMPLE Vll Example 1 is repeated except that the CMC and brighteners are added just before the tripolyphosphate.
- EXAMPLE V111 The procedure of examples [1 and 111 is followed to determine which of the components has an effect on gelation. This is accomplished by elimination of components. It is ascertained that the elimination of either the nonionic detergent, the quaternary ammonium salt or the phosphate from the crutching formula results in no gelation.
- a process for preparing a spraydricd granular softenerdetergcnt composition consisting essentially of (a) about 2 percent to about 8 percent by weight ofa quaternary ammonium textile softener represented by the general formula It: t
- R and R are alkyl groups each containing from 1 to 3 carbon atoms; R and R are alkyl groups each containing from 12 to 22 carbon atoms; and X is selected from the group consisting of chlorine, bromine, and methyl sulfate; (12) about 5 percent to 30 percent by weight of a water-soluble nonionic detergent having a hydrophobic group of 8 to 30 carbon atoms condensed with 5 to 30 moles of ethylene oxide; (c) about 20 percent to 65 percent of a sodium or potassium inorganic phosphate builder salt; and (d) 5 to 15 percent water which comprises the steps of: l admixing water, said nonionic detergent, and quaternary ammonium softener to form an aqueous mixture wherein the quaternary softener is homogeneously dispersed; (2) introducing a sodium or potassium inor ganic phosphate builder salt into said aqueous mixture whereby a mixture containing more than
- at least one water-soluble inorganic diluent selected from the group consisting of sodium sulfate, potassium sulfate, sodium carbonate, sodium chloride and sodium silicate is introduced prior to, simultaneously with, or after said introduction of said phosphate, the amount of said diluent being sufficient to provide 10 to 37.5 percent by weight of said diluent in the spraydried product.
- phosphate builder salt is sodium or potassium tripolyphosphate.
- a process in accordance with claim 9 wherein the mixture formed and spray dried contains about 59 percent to about 65 percent solids by weight.
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Abstract
A process for the preparation of a spray-dried, built, detergent-softener composition containing an ethoxylated nonionic detergent in combination with a di-higher alkyl quaternary ammonium textile softener is described which comprises the steps of (1) admixing the softener, nonionic detergent, and water to form an aqueous mixture containing a homogeneous dispersion of the softener; (2) incorporating an inorganic sodium or potassium phosphate builder in the aqueous mixture of step 1 to form a mixture containing more than 50 percent solids by weight, the temperature of the mixture being at least about 180* F. at the time the phosphate is introduced therein, and (3) spray drying the mixture of step 2.
Description
United States Patent New York, N.Y. Continuation-impart of application Ser. No. 587,364, Sept. 26, 1966, now abandoned.
PROCESS FOR THE PREPARATION OF LAUNDERING COMPOSITIONS 10 Claims, No Drawings U.S. Cl 252/137, 252/152 Int. Cl Clld 1/62, Cl ld l/86,C1 1d 3/06 Field of Search 252/137, 152, 99
References Cited UNITED STATES PATENTS 3,325,4l4 6/1967 lnamorato 252/l52X 3,360,470 12/1967 Wixon 252/l52X ABSTRACT: A process for the preparation of a spray-dried, built, detergent-softener composition containing an ethoxylated nonionic detergent in combination with a di-higher alkyl quaternary ammonium textile softener is described which comprises the steps of( l admixing the softener, nonionic dctergent, and water to form an aqueous mixture containing a homogeneous dispersion of the softener; (2) incorporating an inorganic sodium or potassium phosphate builder in the aqueous mixture of step i to form a mixture containing more than 50 percent solids by weight, the temperature of the mixture being at least about 180 F. at the time the phosphate is introduced therein, and (3) spray drying the mixture of step 2.
PROCESS FOR THE PREPARATION OF LAUNDERING COMPOSITIONS This is a continuation of Ser. No. 587,364, filed Sept. 26, 1966, now abandoned.
A PROCESS FOR THE PREPARATION OF LAUNDERING COMPOSITIONS This invention relates to the preparation of laundering compositions and more particularly to a process for preparing spray-dried granular laundering compositions.
The application of Harold Eugene Wixon filed Aug. 2, I966 bearing Ser. No. 576,493 entitled LAUNDERING COMPOSI- TIONS, now US. Pat. No. 3,360,470, which is incorporated by reference herein, concerns itself with a novel composition comprising a quaternary ammonium textile softener and an alkali metal carboxymethylcellulose. The function of the softening agent is to render fabrics and textiles soft" with respect to handle, hand, touch, or feel. However, due to the presence of colored colloidal particles in most water supplies, these cationic softening agents, while softening, have a tendency to yellow fabrics and, therefore an antiyellowing agent, i.e., the alkali metal carboxymethylcellulose, is introduced in sufficient amount to inhibit the yellowing effect. This particular softener composition can be used together with a detergent composition in the wash cycle rather than having it introduced in the rinse cycle, which is generally the case with fabric softeners.
The practice has been to form the components of the softener composition into granules and mix these granules with detergent composition granules to produce a commercial package. This is usually accomplished by using a three-step process, which merely means that the softener granules and the detergent granules are prepared separately by crutching and spray drying and the two kinds of granules are subsequently blended to produce the product. The three-step" process as the term is used in the industrial sense is not given a literal interpretation. Actually, the first two steps are complete processes within themselves for crutching and spray-drying a particular composition, in this case a softener or detergent composition. The third step is concerned with the blending of the two components.
Although the three-step process produced a satisfactory product, it was uneconomical in that either two sets of crutching and spray-drying equipment were needed if preparation of the softener and detergent granules was to take place simultaneously or, in the alternative, the preparation time had to be extended if the same equipment was to be used first for one type of granule and then for the other type of granule. In both cases, of course, a blending machine was still necessary to mix the granules. It can be readily seen that the elimination of one of the crutching-spray drying procedures and the blending step not only would save equipment but would save time solids eliminate some material waste.
A one-step process was then attempted in order to eliminate the need for extra equipment and cut the process time by preparing the softener and detergent in a form whereby each granule contained by proportionate share of softener and detergent. It was felt that this process would also reduce segregation and contribute to a higher uniformity of product.
In order to carry out the one-step process, softener and detergent components as disclosed in U.S. Pat. No. 3,360,470 referred to above, were mixed in a crutcher under the assumption that after crutching, the mixture of components could then be spray-dried in a conventional manner; however, it was found that when more than 47 percent solids (by weight based on the total weight of the ingredients introduced into the crutcher) were present in the crutcher substantially irreversi ble gelation occurred to the extent that spray drying could not be effected. The one-step" process was, therefore, unfeasible in an industry where generally more than 47 percent solids and preferably about 59 or 60-65 percent solids must be spray-dried in order to produce an economical product. In
view of the problem of gelation, it became apparent that it was more economical to prepare a softener-detergent product from the foregoing three-step" process than to use a onestep" process with 47 percent or less solids, especially in view of the fact that the gelation was found to be substantially irreversible even though water dilution and heating were applied to break the gel.
It is, therefore, an object of this invention to provide an economical one-step process for the preparation of spraydried softener-detergent granules based on an amount of crutcher solids which is more than 47 percent by weight and preferably about 59 to about 65 percent by weight.
A further object is to provide a process whereby the spraydried softener-detergent granules are such that the softener and detergent compositions are combined in each granule in a homogeneous relationship.
Other objects and advantages will become apparent from the following description of the invention.
In accordance with the invention, a one-step process has been found for preparing a spray-dried granular softener-detergent composition wherein each granule is composed of a homogeneous mixture of softener-detergent components comprising:
a. admixing water, a water-soluble nonionic detergent, and a quaternary ammonium salt at a temperature of at least 180 F., wherein the quaternary salt is homogeneously dispersed therein and the mixture contains more than 47 percent solids by weight;
b. introducing an alkali metal phosphate builder into the mixture; and
c. spray-drying the mixture.
It is preferred that at or about the time of introduction of the alkali metal phosphate, during step (b) an inorganic water soluble diluent to provide bulk and an alkali carboxymethyl' cellulose as an antiyellowing agent, be added. So long as the temperature of the mixture is at least 180 F., and the quaternary salt is dispersed, the order of addition of the alkali metal phosphate and the inorganic water soluble diluent (elec trolytes) is immaterial. The alkali metal carboxymethylcellulose can be added at any point of the process.
The spray-dried product of this invention has been found exceptionally satisfactory in the following parameters: solubility, free flow, low dust content, storage, narrow distribution of particle sizes, bulk density, residual moisture content, and color. The granules, which, as previously mentioned, contain a homogeneous mixture of softener-detergent composition, are hollow and have sufficient strength to resist the stress and strain of handling which take place throughout the processing, packaging, and delivery stages of their commercial life. The final cup weight of the commercial product is preferably from about 60 to 125 grams, flowability about 70 percent to about percent, and particle size about 16 to about 60 mesh. Cup weight is based on a cup which holds 237 grams of water.
A more detailed description of the process of this invention follows:
The first part of the process is carried out in conventional crutching apparatus wherein initially water, a water-soluble nonionic detergent, and a quaternary ammonium salt are introduced simultaneously or in any order which is desirable to the operator. The preferred order is that stated.
All of the conventional water-soluble nonionic detergents can be used in the process of this invention, but are preferably in liquid or paste form. Generally, such nonionics have a hydrophobic group containing at least 8 to 30 carbon atoms. One particular class of such detergents is that formed by the oxyalkylation of fatty acids, alcohols, phenols, mercaptans, thiophenols, amines, and with ethylene oxide, propylene oxide, and other related alkylene oxides. Such materials usually have at least 5 mols of alkylene oxide, and preferably 5 to 30 mols of alkylene oxide, depending upon the particular hydrophobic group desired. Representative of these materials are those formed by condensation of ethylene oxide with alkyl phenols or alcohols. Particularly preferred herein are condensates formed by the reaction of one mol of nonyl phenol or a mixture of C -C saturated, straight-chain, aliphatic alcohols with 8 to l2mo1s of ethylene oxide, the condensates containing an average of about 8 to ethylene oxide groups per molecule. Some specific examples of this type of nonionic detergent are as follows: nonyl phenol-ethylene oxide condensates having an average of 9.5 ethylene oxide groups per molecule; a mixture of saturated aliphatic alcohols having from 14 carbons to l8 carbons in their chains and an average of 8.5 mols of ethylene oxide per molecule; tallow alcoholethylene oxide condensate having an average of 9 mols of ethylene oxide per molecule; and a 1:1 mixture of a C and a C saturated aliphatic alcohol having an average of 8.5 mols of ethylene oxide per molecule. Other alkylphenol condensates are those of diamylphenol, p-tert-octylphenol, 2,4- dicyclohexylphenol, m-pentadecylphenol, and benzyl-ohydroxybiphenyl. Other condensates with alkylene oxide are those of tall oil, branched chain C to C,-, aliphatic alcohols, lanolin, beeswax, bis-phenols, oxidized paraffin wax, napthenic acids, and fatty acyl alkanolamides. Mixtures of various water soluble nonionic detergents are contemplated.
The quaternary ammonium slat softener can be exemplified by the following general formula:
wherein R and R are alkyl groups each containing from 1 to 3 carbon atoms; R and R are aliphatic groups each containing from 12 to 22 carbon atoms; and X is selected from the group consisting of chlorine, bromine, and methyl sulfate. These compounds are readily dispersible in water. Specific examples are as follows: distearyl dimethyl quaternary ammonium chloride; distearyl dimethyl quaternary ammonium bromide; distearyl dimethyl quaternary ammonium methylsulfate; dicoco dimethyl quaternary ammonium chloride; dimethyl arachidyl behenyl quaternary ammonium chloride; dialkyl dimethyl quaternary ammonium chloride, the alkyl groups of which comprise a mixture consisting essentially of 24 parts hexadecyl 75 parts octadecyl and 1 part octadecenyl groups; the latter quaternary ammonium chloride is also known as dimethyl dihydrogenated ditallow ammonium chloride and is particularly preferred. Mixture of two or more cationic softener agents can be employed if desired. (The term coco" refers to fatty acid groups formed in coconut oil fatty acids. Such acids contain from about 8 to about 18 carbon atoms per molecule, predominating in C C acids). Other examples are dimethyl ditallow hydrazinium chloride and dimethyl ditallow quaternary ammonium methyl sulfate.
The proportions of the foregoing components which can be used are as follows: waterabout 33 percent to about 43 percent and preferably about 35 percent to about 41 percent; nonionic detergentabout 3.5 percent to about percent and preferably about 4.5 percent to about 8.5 percent; quaternary ammonium salt-about 1 percent to about 6 percent and preferably about 2.5 to about 4 percent. These percentages are by weight and based on the total weight of the initial materials as introduced into the crutcher. The proportions of the other components will be set forth below.
It is important that the quaternary ammonium salt be homogeneously dispersed in the mixture before the phosphate builder is added. This is accomplished by heating or agitation caused by merely admixing the water, nonionic, and quaternary salt or by external means. Both agitation and heating are discussed below. The homogeneous dispersion of the quaternary ammonium salt bears a similarity to a melt or solution of the salt in the water and nonionic.
Agitation, which is preferred and practical, can be initiated before, during, or after the water, nonionic detergent, and quaternary ammonium salt are introduced into the crutcher.
The speed of agitation can range from about 100 revolutions per minute (r.p.m.) to about 500 r.p.m. and preferably from about r.p.m. to about 400 r.p.m. and can be varied during the course of the process. The given rates are based on the used of conventional equipment. Actually, any reasonable movement or agitation of the mixture will suffice to carry out the process of this invention so long as it commences before or at the same time as the addition of the second group of components, although high shear agitation is not practical.
Before introduction of the phosphate, the materials in the crutcher should be a temperature of at least about 180 F. It is preferred to initially heat the first group of materials (water, nonionic, and quaternary salt) about 130 F. to about F; however, there is no prohibition against raising the temperature at any time before the second group of materials is added. The particular mode of heating is not important and can be accomplished with whatever heating apparatus is available so long as the temperature can be ascertained. Once the temperature of the mixture has been raised to at least 180 F. and the quaternary salt is homogeneously dispersed, the second group of components can be introduced into the crutcher. There is actually no upper limit for the temperature of heating the crutcher materials other than keeping the temperature below the boiling point of water (212 F.). However, the most practical temperatures are from about 180 F. to about 200 F. and preferably from about 180 F. to about 190 F. If the ternperature is less than 180 F. and particularly about F. or less, gelation occurs after one or more of the second group of components is introduced to obtain more than 47 percent solids. It should be noted that between 175 F. and below about F. there is a gray area in which gelation is not sharply apparent, but is sufficient to hamper economical spray-drying. By heating to at least about 180 F., this partial gelation is also avoided.
Once the proper temperature has been attained, and the quaternary salt homogeneously dispersed, the alkali metal phosphate, the inorganic water-soluble diluent, and the alkali metal carboxymethylcellulose can be introduced into the crutcher. Just as the first group of components, this second group has no particular order of introduction and each component can be introduced one at a time or the entire group can be added simultaneously, although preferably the order stated is the order followed. Agitation can be continued until a homogeneous mixture is attained.
Examples of the alkali metal phosphate builder salts are the alkali metal tripolyphosphates and pyrophosphates of which the sodium and potassium compounds are most commonly used. These phosphates are well known in the detergent art as builders and can either be used alone or as mixtures of different phosphates. More specific examples of phosphate builder salts are as follows; sodium tripolyphosphate; sodium phosphate, tribasic; sodium phosphate, monobasic; sodium phosphate, dibasic, sodium pyrophosphate; sodium pyrophosphate; acid. The corresponding potassium salts are also examples of satisfactory builders for use herein along with mixtures of the salts or corresponding mixed potassium-sodium salts.
Of the tripolyphosphates, a low phase l material is preferred, i.e., a phase 2 tripolyphosphate associated with a maximum of about 8 percent phase 1 tripolyphosphate, the phase 1 crystalline form being a high temperature rise material with hydrates more rapidly than the phase 2 material. The preferred tripolyphosphate form is conventional for spray dry ing operation and was used in Example I, below.
In order to give bulk to the composition, an inorganic water soluble diluent can be used which is exemplified by the preferred alkali metal (generally Na or K) sulfates such as sodium sulfate. These preferred diluents generally do not provide any substantial detersive activity. Other examples of diluents are sodium chloride and sodium carbonate. Diluents such as the silicates exemplified by sodium metasilicate and sodium silicates wherein the ratio of Na O to SiO is from about 1.621 to about 3.2:1; borax; clays such as kaolin, the montmorillonites, and bentonites; silica sol; titanium oxide; colloidal aluminum hydroxide; and ammonium carbonate can also be used; however, it is preferred that the major proportion of the diluent be an alkali metal sulfate, which can be considered an inert material.
The third component of the second group is an alkali metal (generally, Na or K) carboxymethylcellulose, in particular those having about 0.5 to about 0.8 carboxymethyl group per cellulose unit. This component is considered an organic builder and as noted in U.S. Pat. No. 3,360,470 referred to above provides the antiyellowing efiect for the quaternary ammonium softener.
The proportions of the second group of components which are by weight based on the total weight of components introduced into the crutcher are as follows: alkali metal phosphate builder salt-about 13 percent to about 45 percent and preferably 27 percent to 33 percent; dilventabout 7 percent to about 25 percent and preferably 17 percent to about 23 percent; and an alkali metal carboxymethylcellulose about 0.3 percent to about 4.5 percent and preferably about 0.7 percent to about 2.5 percent.
In addition to the stated proportions, the proportions should be selected in a corresponding ratio so that there will be a sufficient amount of each component to provide more than 47 percent solids in the crutcher composition. it should be noted that even through 59-60to 65 percent solids are generally considered the most desirable for spray-drying, all of the solids percentages above 47 percent and preferably about 50 percent are important because the bulk density of the composition after spray-drying is dependent upon the percentage of solids resulting from the crutching operation. Although it is not generally the case, there are some instances when it is commercially necessary to achieve a bulk density which will result from a lower solids percentage. However, this does not in any case normally go below the 50 percent solids level. About 65 percent solids is the upper practical limit for spraydrying because the high solids content becomes too difficult to pump; however, higher levels of solids can be crutched within the process of this invention, if desired.
Crutching time is generally from about 5 minutes to an hour or more with about 20 to 40 minutes being most desirable. Time is not critical and it has been found that about 30 minutes provides satisfactory homogeneity. Times greater than an hour provide no advantage and shorter than 5 minutes contribute to waste because of settling.
The spray-drying equipment used is just as conventional as the crutching equipment. It includes spray nozzles, a high pressure pump, an air spray system, a heater for the air, and a dust separator. Two types of systems make use of this equipment. They are known as parallelcurrent and countercurrent drying and of these two systems the countercurrent system is the most desirable; however, in many cases, both systems are used to take advantage of each.
Conventional colorants, perfumes, brighteners, and bluing agents can be added if desired. The amounts of these substances introduced into the softener-detergent composition are obviously such that they will not adversely affect the desired properties. The amounts of all of these substances taken together add up to less than 2 percent by weight of the total weight of the crutcher composition and preferably less than 1 percent. The colorants are usually in the form of dyes. Examples of the brighteners are stilbene, triazole, and benzidine sulfone compositions, the stilbene and triazole compositions in combination being preferred. These components are, of course, not an essential part of the softener-detergent composition used in the process of this invention. The colorant and perfume are preferably added during or after spray-drying whereas the brighteners are added to the crutcher mixture. The bluing agent is usually added to the crutcher mixture after the water and it is a preferred component because of its antiyellowing contribution. An example of a bluing agent is ultramarine blue which has been found to be stable to light, alkali, and bleach and is insoluble in water. Ultramarine blue is a well-known blue pigment occurring naturally as the mineral lapis lazuli and can be synthesized by igniting a mixture of kaolin, sodium carbonate or sulfate, sulfur, and carbon. The micropulverized, synthetic ultramarine blues have proved satisfactory.
The proportions of components which can be present in the final product in percent by weight based on the total weight of the final composition are as follows: waterabout 5 percent to about 15 percent and preferably about 6.5 percent to about 12.5 percent; nonionic detergentabout 5 percent to about 30 percent and preferably about 7 percent to about l2 percent; quaternary ammonium salt-about 2 percent to about 8 percent and preferably about 4 percent to about 6 percent; alkali metal phosphate builder salts about 20 percent to about 65 percent and preferably about 40 percent to about 48percent; dilventabout 10 percent to about 37.5 percent and preferably about 25 percent to about 35percent; an alkali metal carboxymethylcelluloseabout 0.5 percent to about 5.33 percent and preferably about 1 percent to about 3.5 percent; colorant, perfumes, brighteners, and bluing agentstotal weight 0 percent to about 2 percent and preferably 0 percent to about 1 percent; bleaching agent-0 percent to about 10 percent and preferably 0 percent to about 5 percent.
The following examples are illustrative of the invention. Parts and percentages are by weight.
EXAMPLE I The following crutcher formula (59.5 percent solids) was used in this example and the components were introduced in consecutive order as numbered:
Percent in Final Component Percent in Crutcher S ray-dried Product I. water (exclusive of 37.640
water mentioned below) 2. ultramarine blue 3. nonionic detergent (nnnyl phenol--ethylene oxide condensate having an average of 9 ethylene oxide groups er molecule) softener (dimethyl dihydrogenated ditallow quaternary ammonium chloride) anhydrous sodium sulfate .a 43.5 percent solution of sodium silicate in water; ratio of Na, to SiO, is 2.35:]
(silicate) sodium tripolyphosphate 29.735
. a 75 ercent dispersion of sodium carboxymethylcellulose (CMC) in water (CMC) 9. a stilbene brightener 10. a triazole brightener agitation (350 rpm), after which the CMC and the brighteners were added. The crutching time was 30 minutes.
The slurry was then pumped with a triplex pump into a spray tower where it was met with a countercurrent of hot air. The dried particles dropped to a conveyor and were transported to an air lift, which passed the granules along to a separator. Screening, perfuming, and packaging followed.
The spray tower conditions were as follows:
tower inlet air temperature SUP-520 F. tower outlet air temperature l85-269 1-. nozzle size 10 number of noulcs 4 triplex pressure 660 p.s.i.g. Productcup weight 81-100 grams The spray-dried product was found to perform well in softening and laundering.
EXAMPLE 11 The same crutcher steps and conditions as in example 1 are followed except the order of addition was water, blue, sulfate, silicate, tripolyphosphate, nonionic detergent, CMC and brighteners, and quaternary ammonium salt. Agitation is used for all ingredients except the nonionic detergent. The 180 F. temperature was invoked before the addition of sulfate.
This procedure produces gelation EXAMPLE 111 The same crutcher steps and conditions prevalent in example l are followed except that instead of 180 F., a temperature of 175 F. is used.
This procedure produces a gelation EXAMPLE [V The same crutcher steps and conditions are followed as in examples 11 and 111 except that in each case proportions are adjusted to reduce the level of crutcher solids to 47 percent.
No gelation occurs.
EXAMPLE V The same crutcher steps and conditions are followed as in example 1 except that proportions are adjusted to reduce the level of crutcher solids to 50 percent.
No gelation occurs.
EXAMPLE Vl Example 1 is repeated except that the proportions are adjusted to obtain 65 percent solids.
No gelation occurs.
EXAMPLE Vll Example 1 is repeated except that the CMC and brighteners are added just before the tripolyphosphate.
No gelation occurs.
EXAMPLE V111 The procedure of examples [1 and 111 is followed to determine which of the components has an effect on gelation. This is accomplished by elimination of components. It is ascertained that the elimination of either the nonionic detergent, the quaternary ammonium salt or the phosphate from the crutching formula results in no gelation.
We claim:
1. A process for preparing a spraydricd granular softenerdetergcnt composition consisting essentially of (a) about 2 percent to about 8 percent by weight ofa quaternary ammonium textile softener represented by the general formula It: t
l lh N-Ri X- wherein R and R are alkyl groups each containing from 1 to 3 carbon atoms; R and R are alkyl groups each containing from 12 to 22 carbon atoms; and X is selected from the group consisting of chlorine, bromine, and methyl sulfate; (12) about 5 percent to 30 percent by weight of a water-soluble nonionic detergent having a hydrophobic group of 8 to 30 carbon atoms condensed with 5 to 30 moles of ethylene oxide; (c) about 20 percent to 65 percent of a sodium or potassium inorganic phosphate builder salt; and (d) 5 to 15 percent water which comprises the steps of: l admixing water, said nonionic detergent, and quaternary ammonium softener to form an aqueous mixture wherein the quaternary softener is homogeneously dispersed; (2) introducing a sodium or potassium inor ganic phosphate builder salt into said aqueous mixture whereby a mixture containing more than 50 percent of solids is formed, the temperature of the mixture being at least about 180 F. and below 212 F. at the time said phosphate is introduced therein; and (3) spray drying the mixture of step 2.
2. A process in accordance with claim 1 wherein said water, said nonionic, and said softener are admixed at a temperature in the range of about F. to about F. and the temperature of said mixture is raised to at least about F. prior to the introduction of said phosphate.
3. A process in accordance with claim 1 wherein said water, said nonionic, and said softener are admixed at a temperature ofat least 180 F.
4. A process in accordance with claim 1 wherein at least one water-soluble inorganic diluent selected from the group consisting of sodium sulfate, potassium sulfate, sodium carbonate, sodium chloride and sodium silicate is introduced prior to, simultaneously with, or after said introduction of said phosphate, the amount of said diluent being sufficient to provide 10 to 37.5 percent by weight of said diluent in the spraydried product.
5. A process in accordance with claim 1 wherein a sodium or potassium carboxymethylcellulose salt is introduced prior to, simultaneously with or after said introduction of said phosphate, the amount of said cellulose being sufficient to provide 0.5 to about 5.33 percent by weight of said cellulose in the spray-dried product.
6. A process in accordance with claim 1 wherein the temperature of the mixture of step 1 is about 180 F. to about F. at the time said phosphate is introduced.
7. A process in accordance with claim 1 wherein said phosphate builder salt is sodium or potassium tripolyphosphate.
8. A process in accordance with claim 4 wherein said diluent is sodium or potassium sulfate.
9. A process in accordance with claim 8 wherein said sulfate is added after said phosphate salt and a sodium or potassium carboxymethylcellulose is introduced thereafter, the amount of said cellulose being sufficient to provide 05 percent to about 5.33 percent by weight thereof in the spray-dried product. l
10. A process in accordance with claim 9 wherein the mixture formed and spray dried contains about 59 percent to about 65 percent solids by weight.
Claims (9)
- 2. A process in accordance with claim 1 wherein said water, said nonionic, and said softener are admixed at a temperature in the range of about 130* F. to about 160* F. and the temperature of said mixture is raised to at least about 180* F. prior to the introduction of said phosphate.
- 3. A process in accordance with claim 1 wherein said water, said nonionic, and said softener are admixed at a temperature of at least 180* F.
- 4. A process in accordance with claim 1 wherein at least one water-soluble inorganic diluent selected from the group consisting of sodium sulfate, potassium sulfate, sodium carbonate, sodium chloride and sodium silicate is introduced prior to, simUltaneously with, or after said introduction of said phosphate, the amount of said diluent being sufficient to provide 10 to 37.5 percent by weight of said diluent in the spray-dried product.
- 5. A process in accordance with claim 1 wherein a sodium or potassium carboxymethylcellulose salt is introduced prior to, simultaneously with or after said introduction of said phosphate, the amount of said cellulose being sufficient to provide 0.5 percent to about 5.33 percent by weight of said cellulose in the spray-dried product.
- 6. A process in accordance with claim 1 wherein the temperature of the mixture of step 1 is about 180* F. to about 190* F. at the time said phosphate is introduced.
- 7. A process in accordance with claim 1 wherein said phosphate builder salt is sodium or potassium tripolyphosphate.
- 8. A process in accordance with claim 4 wherein said diluent is sodium or potassium sulfate.
- 9. A process in accordance with claim 8 wherein said sulfate is added after said phosphate salt and a sodium or potassium carboxymethylcellulose is introduced thereafter, the amount of said cellulose being sufficient to provide 0.5 percent to about 5.33 percent by weight thereof in the spray-dried product.
- 10. A process in accordance with claim 9 wherein the mixture formed and spray dried contains about 59 percent to about 65 percent solids by weight.
Applications Claiming Priority (1)
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US87898969A | 1969-12-05 | 1969-12-05 |
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US3607763A true US3607763A (en) | 1971-09-21 |
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US878989A Expired - Lifetime US3607763A (en) | 1969-12-05 | 1969-12-05 | Process for the preparation of laundering compositions |
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Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2334899A1 (en) * | 1972-07-14 | 1974-01-24 | Procter & Gamble | GRAINY DETERGENT COMPOSITION |
DE2406553A1 (en) * | 1973-02-16 | 1974-08-29 | Procter & Gamble | FABRIC SOFTENING MIXTURES AND DETERGENT MIXTURES CONTAINING THESE |
DE2439541A1 (en) * | 1973-08-24 | 1975-03-06 | Procter & Gamble | GRAINY DETERGENT COMPOSITION |
FR2340984A1 (en) * | 1976-02-10 | 1977-09-09 | Unilever Nv | PROCESS FOR PREPARING DETERGENT COMPOSITIONS |
EP0000234A1 (en) * | 1977-06-29 | 1979-01-10 | THE PROCTER & GAMBLE COMPANY | Low-phosphate detergent composition for fabric washing |
EP0000235A1 (en) * | 1977-06-29 | 1979-01-10 | THE PROCTER & GAMBLE COMPANY | Low-phosphate detergent composition for fabric washing |
US4196104A (en) * | 1977-09-26 | 1980-04-01 | The Procter & Gamble Company | Process for producing antistatic, fabric-softening detergent composition |
US4199465A (en) * | 1977-12-23 | 1980-04-22 | The Procter & Gamble Company | Laundry detergent substrate articles |
US4199464A (en) * | 1977-12-23 | 1980-04-22 | The Procter & Gamble Company | Laundry detergent substrate articles |
US4222905A (en) * | 1978-06-26 | 1980-09-16 | The Procter & Gamble Company | Laundry detergent compositions having enhanced particulate soil removal performance |
US4228044A (en) * | 1978-06-26 | 1980-10-14 | The Procter & Gamble Company | Laundry detergent compositions having enhanced particulate soil removal and antiredeposition performance |
US4228042A (en) * | 1978-06-26 | 1980-10-14 | The Procter & Gamble Company | Biodegradable cationic surface-active agents containing ester or amide and polyalkoxy group |
US4239660A (en) * | 1978-12-13 | 1980-12-16 | The Procter & Gamble Company | Detergent composition comprising a hydrolyzable cationic surfactant and specific alkalinity source |
US4259217A (en) * | 1978-03-07 | 1981-03-31 | The Procter & Gamble Company | Laundry detergent compositions having enhanced greasy and oily soil removal performance |
US4265772A (en) * | 1978-11-16 | 1981-05-05 | The Procter & Gamble Company | Antistatic, fabric-softening detergent additive |
US4291071A (en) * | 1978-06-20 | 1981-09-22 | The Procter & Gamble Company | Washing and softening compositions |
FR2495141A1 (en) * | 1980-10-10 | 1982-06-04 | Lilachim Sa | MIXTURES OF QUATERNARY AMMONIUM SALTS AND USE AS A TEXTILE SOFTENER |
US4339335A (en) * | 1976-12-02 | 1982-07-13 | Colgate Palmolive Co. | Free flowing high bulk density particulate detergent-softener |
DE3324057A1 (en) * | 1982-07-05 | 1984-01-12 | Lion Corp., Tokyo | ADDITIONAL FOR GRAINY DETERGENTS AND CLEANERS |
US4493773A (en) * | 1982-05-10 | 1985-01-15 | The Procter & Gamble Company | Low phosphate, softening laundry detergent containing ethoxylated nonionic, alkylpolysaccharide and cationic surfactants |
FR2569717A1 (en) * | 1984-09-04 | 1986-03-07 | Colgate Palmolive Co | Laundry softener-detergent compsns. |
US4661289A (en) * | 1984-08-29 | 1987-04-28 | Lever Brothers Company | Detergent compositions |
US4664817A (en) * | 1980-03-27 | 1987-05-12 | The Colgate-Palmolive Co. | Free flowing high bulk density particulate detergent-softener |
US5147633A (en) * | 1989-12-01 | 1992-09-15 | Ici Renory Sa/Nv | Alkyl sulphate salts |
US5466394A (en) * | 1994-04-25 | 1995-11-14 | The Procter & Gamble Co. | Stable, aqueous laundry detergent composition having improved softening properties |
US5622925A (en) * | 1994-04-25 | 1997-04-22 | The Procter & Gamble Company | Stable, aqueous laundry detergent composition having improved softening properties |
US5672474A (en) * | 1991-05-09 | 1997-09-30 | Streck Laboratories, Inc. | White blood cell hematology control |
-
1969
- 1969-12-05 US US878989A patent/US3607763A/en not_active Expired - Lifetime
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
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DE2334899A1 (en) * | 1972-07-14 | 1974-01-24 | Procter & Gamble | GRAINY DETERGENT COMPOSITION |
DE2406553A1 (en) * | 1973-02-16 | 1974-08-29 | Procter & Gamble | FABRIC SOFTENING MIXTURES AND DETERGENT MIXTURES CONTAINING THESE |
DE2439541A1 (en) * | 1973-08-24 | 1975-03-06 | Procter & Gamble | GRAINY DETERGENT COMPOSITION |
FR2340984A1 (en) * | 1976-02-10 | 1977-09-09 | Unilever Nv | PROCESS FOR PREPARING DETERGENT COMPOSITIONS |
US4126586A (en) * | 1976-02-10 | 1978-11-21 | Lever Brothers Company | Process of spray drying nonionic surfactant-containing detergents also containing a cationic nitrogen compound |
US4339335A (en) * | 1976-12-02 | 1982-07-13 | Colgate Palmolive Co. | Free flowing high bulk density particulate detergent-softener |
EP0000234A1 (en) * | 1977-06-29 | 1979-01-10 | THE PROCTER & GAMBLE COMPANY | Low-phosphate detergent composition for fabric washing |
EP0000235A1 (en) * | 1977-06-29 | 1979-01-10 | THE PROCTER & GAMBLE COMPANY | Low-phosphate detergent composition for fabric washing |
US4196104A (en) * | 1977-09-26 | 1980-04-01 | The Procter & Gamble Company | Process for producing antistatic, fabric-softening detergent composition |
US4199465A (en) * | 1977-12-23 | 1980-04-22 | The Procter & Gamble Company | Laundry detergent substrate articles |
US4199464A (en) * | 1977-12-23 | 1980-04-22 | The Procter & Gamble Company | Laundry detergent substrate articles |
US4259217A (en) * | 1978-03-07 | 1981-03-31 | The Procter & Gamble Company | Laundry detergent compositions having enhanced greasy and oily soil removal performance |
US4291071A (en) * | 1978-06-20 | 1981-09-22 | The Procter & Gamble Company | Washing and softening compositions |
US4222905A (en) * | 1978-06-26 | 1980-09-16 | The Procter & Gamble Company | Laundry detergent compositions having enhanced particulate soil removal performance |
US4228044A (en) * | 1978-06-26 | 1980-10-14 | The Procter & Gamble Company | Laundry detergent compositions having enhanced particulate soil removal and antiredeposition performance |
US4228042A (en) * | 1978-06-26 | 1980-10-14 | The Procter & Gamble Company | Biodegradable cationic surface-active agents containing ester or amide and polyalkoxy group |
US4265772A (en) * | 1978-11-16 | 1981-05-05 | The Procter & Gamble Company | Antistatic, fabric-softening detergent additive |
US4239660A (en) * | 1978-12-13 | 1980-12-16 | The Procter & Gamble Company | Detergent composition comprising a hydrolyzable cationic surfactant and specific alkalinity source |
US4664817A (en) * | 1980-03-27 | 1987-05-12 | The Colgate-Palmolive Co. | Free flowing high bulk density particulate detergent-softener |
FR2495141A1 (en) * | 1980-10-10 | 1982-06-04 | Lilachim Sa | MIXTURES OF QUATERNARY AMMONIUM SALTS AND USE AS A TEXTILE SOFTENER |
US4493773A (en) * | 1982-05-10 | 1985-01-15 | The Procter & Gamble Company | Low phosphate, softening laundry detergent containing ethoxylated nonionic, alkylpolysaccharide and cationic surfactants |
DE3324057A1 (en) * | 1982-07-05 | 1984-01-12 | Lion Corp., Tokyo | ADDITIONAL FOR GRAINY DETERGENTS AND CLEANERS |
US4627927A (en) * | 1982-07-05 | 1986-12-09 | Lion Corporation | Additive composition for granular detergent |
US4661289A (en) * | 1984-08-29 | 1987-04-28 | Lever Brothers Company | Detergent compositions |
FR2569717A1 (en) * | 1984-09-04 | 1986-03-07 | Colgate Palmolive Co | Laundry softener-detergent compsns. |
US5147633A (en) * | 1989-12-01 | 1992-09-15 | Ici Renory Sa/Nv | Alkyl sulphate salts |
US5672474A (en) * | 1991-05-09 | 1997-09-30 | Streck Laboratories, Inc. | White blood cell hematology control |
US5466394A (en) * | 1994-04-25 | 1995-11-14 | The Procter & Gamble Co. | Stable, aqueous laundry detergent composition having improved softening properties |
US5622925A (en) * | 1994-04-25 | 1997-04-22 | The Procter & Gamble Company | Stable, aqueous laundry detergent composition having improved softening properties |
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